Interaction of a lithiated nitronyl nitroxide with polyfluorinated 1,4-naphthoquinones

A 4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl lithium derivative was found to react with 2-methoxypentafluoro-1,4-naphthoquinone to form a product of addition at the carbonyl function: radical 2-(3,5,6,7,8-pentafluoro-1-hydroxy-2-methoxy-4-oxo-1,4-dihydronaphthalen-1-yl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl. The yield of the addition product increased with temperature and reached 84% at 0?°C. The reaction of the lithium derivative with hexafluoro-1,4-naphthoquinone gave rise to a product of addition at both carbonyl groups, namely, nitronyl nitroxide diradical 2,3,5,6,7,8-hexafluoro-1,4-bis(4,4,5,5-tetramethyl-3-oxide-1-oxyl-4,5-dihydro-1H-imidazole-2-yl)-1,4-dihydronaphthalene-1,4-diol in a 16% yield. The structures of both mono- and diradical were solved by X-ray diffraction analysis, which revealed formation of an intramolecular H-bond between the OH group and nitroxide oxygen. According to electron paramagnetic resonance (EPR) spectroscopy, the obtained mono- and dinitroxide are prone to spontaneous deoxygenation in a toluene solution to give corresponding iminonitroxides. In water, they are much more stable.     

Characterisation of charge carrier transport in thin organic semiconductor layers by time-of-flight photocurrent measurements

The paper reviews recent advances in characterisation of charge carrier transport in organic semiconductor layers by time-of-flight photocurrent measurements, with the emphasis on the measurements of the samples with co-planar electrodes. These samples comprised an organic semiconductor layer whose thickness is on the order of a μm or less, and thus mimic the structures of organic thin film transistors. In the review we emphasise the importance of considering spatial variation of electric field in these, essentially two-dimensional structures, in interpretation of photocurrent transients. We review the experimental details of this type of measurements and give examples that demonstrate exceptional sensitivity of the method to minute concentration of electrically active defects in the organic semiconductors as well as the capability of probing charge transport along the channels of different mobility that reside in the same sample.     

Ambipolar carrier transport in an optically controllable diarylethene thin film transistor

Ambipolar carrier transport is demonstrated in an optically controllable organic field-effect transistor, where a benzothienothiophene-substituted diarylethene (BTT-DAE) thin film is employed directly as the transistor channel. A closed-ring isomer, which is produced by ultraviolet (UV) light irradiation, allows the carrier injection of both holes and electrons from source-drain electrodes into the BTT-DAE layer. Moreover, alternate UV or visible (VIS) light irradiation induces marked switching in the drain currents caused by reversible photoisomerization between closed-ring (semiconductor) and open-ring (insulator) isomers. The light-driven on/off ratio, which is defined by the ratio of the drain currents in the sample after UV or VIS light irradiation, reaches 240 for hole transport. The value is comparable to the gate-voltage-induced on/off ratio of 160. Our findings, therefore, have a potential to lead to the construction of new optoelectronic devices such as photoreconfigurable logic circuits and light emitting transistors.     

Exploiting In Situ Redox and Diffusion of Molybdenum to Enable Thin‐Film Circuitry for Low‐Cost Wireless Energy Harvesting

Direct additive fabrication of thin‐film electronics using a high‐mobility, wide‐bandgap amorphous oxide semiconductor (AOS) can pave the way for integration of efficient power circuits with digital electronics. For power rectifiers, vertical thin‐film diodes (V‐TFDs) offer superior efficiency and higher frequency operation compared to lateral thin‐film transistors (TFTs). However, the AOS V‐TFDs reported so far require additional fabrication steps and generally suffer from low voltage handling capability. Here, these challenges are overcome by exploiting in situ reactions of molybdenum (Mo) during the solution‐process deposition of amorphous zinc tin oxide film. The oxidation of Mo forms the rectifying contact of the V‐TFD, while the simultaneous diffusion of Mo increases the diode's voltage range of operation. The resulting V‐TFDs are demonstrated in a full‐wave rectifier for wireless energy harvesting from a commercial radio‐frequency identification reader. Finally, by using the same Mo film for V‐TFD rectifying contacts and TFT gate electrodes, this process allows simultaneous fabrication of both devices without any additional steps. The integration of TFTs alongside V‐TFDs opens a new fabrication route for future low‐cost and large‐area thin‐film circuitry with embedded power management.     

Multiaxial and Transparent Strain Sensors Based on Synergetically Reinforced and Orthogonally Cracked Hetero‐Nanocrystal Solids

Wearable strain sensors are widely researched as core components in electronic skin. However, their limited capability of detecting only a single axial strain, and their low sensitivity, stability, opacity, and high production costs hinder their use in advanced applications. Herein, multiaxially highly sensitive, optically transparent, chemically stable, and solution‐processed strain sensors are demonstrated. Transparent indium tin oxide and zinc oxide nanocrystals serve as metallic and insulating components in a metal–insulator matrix and as active materials for strain gauges. Synergetic sensitivity‐ and stability‐reinforcing agents are developed using a transparent SU‐8 polymer to enhance the sensitivity and encapsulate the devices, elevating the gauge factor up to over 3000 by blocking the reconnection of cracks caused by the Poisson effect. Cross‐shaped patterns with an orthogonal crack strategy are developed to detect a complex multiaxial strain, efficiently distinguishing strains applied in various directions with high sensitivity and selectivity. Finally, all‐transparent wearable strain sensors with Ag nanowire electrodes are fabricated using an all‐solution process, which effectively measure not only the human motion or emotion, but also the multiaxial strains occurring during human motion in real time. The strategies can provide a pathway to realize cost‐effective and high‐performance wearable sensors for advanced applications such as bio‐integrated devices.     

A Room‐Temperature High‐Conductivity Metal Printing Paradigm with Visible‐Light Projection Lithography

Fabricating electronic devices require integrating metallic conductors and polymeric insulators in complex structures. Current metal‐patterning methods such as evaporation and laser sintering require vacuum, multistep processes, and high temperature during sintering or postannealing to achieve desirable electrical conductivity, which damages low‐temperature polymer substrates. Here reports a facile ecofriendly room‐temperature metal printing paradigm using visible‐light projection lithography. With a particle‐free reactive silver ink, photoinduced redox reaction occurs to form metallic silver within designed illuminated regions through a digital mask on substrate with insignificant temperature change (<4 °C). The patterns exhibit remarkably high conductivity achievable at room temperature (2.4 × 10⁷ S m^?1, ≈40% of bulk silver conductivity) after simple room‐temperature chemical annealing for 1–2 s. The finest silver trace produced reaches 15 µm. Neither extra thermal energy input nor physical mask is required for the entire fabrication process. Metal patterns were printed on various substrates, including polyethylene terephthalate, polydimethylsiloxane, polyimide, Scotch tape, print paper, Si wafer, glass coverslip, and polystyrene. By changing inks, this paradigm can be extended to print various metals and metal–polymer hybrid structures. This method greatly simplifies the metal‐patterning process and expands printability and substrate materials, showing huge potential in fabricating microelectronics with one system.     

Full 3D Printing of Stretchable Piezoresistive Sensor with Hierarchical Porosity and Multimodulus Architecture

A soft piezoresistive sensor with its unique characteristics, such as human skin, light weight, and multiple functions, yields a variety of possible practical applications to skin‐attachable electronics, human–machine interfaces, and electronic skins. However, conventional filler‐matrix piezoresistive sensors often suffer from unsatisfactory sensitivity or insufficient measurement range, as well as significant cross‐correlation between out‐of‐plane pressure and in‐plane extension. Here, a stretchable piezoresistive sensor (SPS) is realized by combining a hierarchically porous sensing element with a multimodulus device architecture via a full 3D printing process. As a result, the sensor exhibits high sensitivity (5.54 kPa^?1), large measurement range (from 10 Pa to 800 kPa), limited cross‐correlation, and excellent durability. Meanwhile, benefiting from the porous structure and mechanical mismatch design, which efficiently distributes the stress away from the sensing element, the device experiences only 7% resistance change at 50% stretching. This approach is employed to rapidly program and readily manufacture stylish, all‐in‐one, functional devices for various applications, demonstrating that the technique is promising for customized stretchable electronics.     

Dielectric–Semiconductor Interface Limits Charge Carrier Motion at Elevated Temperatures and Large Carrier Densities in a High‐Mobility Organic Semiconductor

The fundamental nature of charge transport in highly ordered organic semiconductors is under constant debate. At cryogenic temperatures, effects within the semiconductor such as traps or the interaction of charge carriers with the insulating substrate (dipolar disorder or Fröhlich polarons) are known to limit carrier motion. In comparison, at elevated temperatures, where charge carrier mobility often also decreases as function of temperature, phonon scattering or dynamic disorder are frequently discussed mechanisms, but the exact microscopic cause that limits carrier motion is debated. Here, the mobility in the temperature range between 200 and 420 K as function of carrier density is explored in highly ordered perylene‐diimide from 3 to 9 nm thin films. It is observed that above room temperature increasing the gate electric field or decreasing the semiconducting film thickness leads to a suppression of the charge carrier mobility. Via X‐ray diffraction measurements at various temperatures and electric fields, changes of the thin film structure are excluded as cause for the observed mobility decrease. The experimental findings point toward scattering sites or traps at the semiconductor–dielectric interface, or in the dielectric as limiting factor for carrier mobility, whose role is usually neglected at elevated temperatures.     

Low‐Voltage Operational,Low‐Power Consuming,and High Sensitive Tactile Switch Based on 2D Layered InSe Tribotronics

Electronics based on layered indium selenide (InSe) channels exhibit promising carrier mobility and switching characteristics. Here, an InSe tribotronic transistor (denoted as w/In InSe T‐FET) obtained through the vertical combination of an In‐doped InSe transistor and triboelectric nanogenerator is demonstrated. The w/In InSe T‐FET can be operated by adjusting the distance between two triboelectrification layers, which generates a negative electrostatic potential that serves as a gate voltage to tune the charge carrier transport behavior of the InSe channel. Benefiting from the surface charging doping of the In layer, the w/In InSe T‐FET exhibits high reliability and sensitivity with a large on/off current modulation of 10⁶ under a low drain–source voltage of 0.1 V and external frictional force. To demonstrate its function as a power‐saving tactile sensor, the w/In InSe T‐FET is used to sense “INSE” in Morse code and power on a light‐emitting diode. This work reveals the promise of 2D material–based tribotronics for use in nanosensors with low power consumption as well as in intelligent systems.     

Biodegradable Frequency‐Selective Magnesium Radio‐Frequency Microresonators for Transient Biomedical Implants

Bioresorbable implantable medical devices show a great potential for applications requiring medical care over well‐defined periods of time. Once their function is fulfilled, such implants naturally degrade and resorb in the body, which eliminates adverse long‐term effects or the need for a secondary surgery to extract the implanted device. Since biodegradable materials are water‐soluble, the fabrication of such transient electronic circuits and devices requires special care and needs to rely solely on dry processing steps without exposure to aqueous solutions. A further challenge is the in vivo powering of medical implants that are only constituted of biodegradable materials. This paper describes the design, fabrication, and testing of radio‐frequency biodegradable magnesium microresonators. To this end, an innovative microfabrication process with minimal exposure to aqueous media is developed to fabricate magnesium‐based, water‐soluble electronic components. It consists of a novel sequence of only three steps: one physical vapor deposition, one photolithography, and one ion beam etching step. The frequency‐selective wireless heating of different resonators is demonstrated. This represents a significant step toward their use as power receivers and microheaters in biodegradable implantable medical devices, for applications such as triggered drug release.